US4083817A - Blends of furan-aldehyde resins with phenolic resins and molded articles produced therefrom - Google Patents

Blends of furan-aldehyde resins with phenolic resins and molded articles produced therefrom Download PDF

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Publication number
US4083817A
US4083817A US05/806,661 US80666177A US4083817A US 4083817 A US4083817 A US 4083817A US 80666177 A US80666177 A US 80666177A US 4083817 A US4083817 A US 4083817A
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US
United States
Prior art keywords
furan
mixture
binder
resin
formaldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/806,661
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English (en)
Inventor
Hugh C. Anderson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qo Chemicals Inc
Original Assignee
Quaker Oats Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Quaker Oats Co filed Critical Quaker Oats Co
Priority to US05/806,661 priority Critical patent/US4083817A/en
Priority to GB12259/78A priority patent/GB1588701A/en
Priority to ES468590A priority patent/ES468590A1/es
Priority to BE1008815A priority patent/BE865739A/xx
Priority to FR7810308A priority patent/FR2394578A1/fr
Priority to DE19782815909 priority patent/DE2815909A1/de
Priority to NL7803778A priority patent/NL7803778A/xx
Priority to LU79407A priority patent/LU79407A1/xx
Application granted granted Critical
Priority to IT48845/78A priority patent/IT1102580B/it
Publication of US4083817A publication Critical patent/US4083817A/en
Priority to ES471856A priority patent/ES471856A1/es
Assigned to CITIBANK, N.A. reassignment CITIBANK, N.A. LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: QO CHEMICALS, INC.,
Assigned to QO CHEMICALS INC. CHICAGO ILLINOIS reassignment QO CHEMICALS INC. CHICAGO ILLINOIS ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: QUAKER OATS COMPANY A CORP OF NJ
Assigned to QO CHEMICALS, INC. reassignment QO CHEMICALS, INC. RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: CITIBANK, N.A.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers

Definitions

  • resoles Such mixture of phenolic alcohols are widely known and used, and are referred to as "resoles". Upon further heating these alcohols, the "resoles" tend to polymerize to form a phenolic resin.
  • the result of an acid catalyzed reaction of less than one mole of aldehyde per mole of phenol is a "novolac" resin, of the following formula: ##STR2## wherein the resin is a mixture of such molecules, and wherein, in respective molecules, N is zero or an integer.
  • the cure of novolac resins is usually carried out by reaction of the resins with hexamethylenetetraamine.
  • resoles can be used to cross link novolacs.
  • furan-formaldehyde resin referred to herein are those that may be formed, for example, by the reaction of an alpha-unsubstituted furan, such as furan itself, with formaldehyde as disclosed in U.S. Pat. No. 4,017,461 issued on Apr. 12, 1977, to Andrew P. Dunlop and Rudy F. Macander.
  • X and Y may be alike or different, and include hydrogen, halogen, alkyl, phenol, alkyl-substituted phenol, halogen substituted phenol, hydroxy alkyl, carboxy alkyl, in which the alkyl substituents have from one to 10 carbons, and wherein R and R' includes hydrogen, or hydroxymethyl.
  • R and R' are predominantly hydrogen, and wherein N is an integer, at least one.
  • R and R' will include greater amounts of hydroxymethyl termination in the resin.
  • Such resins range in viscosity from about 50 cps to more than 100,000 cps with increasing N value and, typically, with increasing levels of hydroxymethyl.
  • the resins are mixes of molecules having different values of N. We have discovered that in accordance with the present invention these resins couple with phenolic resins of the resole type under acidic catalysis conditions.
  • the acids useful as catalysts in accordance with the present invention include any strong acid. However, the aromatic sulfonic acids are most preferred for use as catalyst in accordance with the present invention.
  • liquid catalyst resole-furan formaldehyde resin reaction mixtures in accordance with the present invention are useful as liquid, hardenable binders for use with glass fibers, foundry sand, etc., in the manufacture of composite articles, for example.
  • a silane be included as an ingredient in the binder mixture.
  • Silanes useful in accordance with the present invention can be any organo silicon compound referred to in U.S. Pat. No. 3,737,430 to Brown, et al.
  • other specific examples include the following:
  • any phenolic resin of the resole type is useful in accordance with the present invention.
  • liquid resin which results from less than completion of the coupling reaction is useful as a binder for producing foundry sand shapes.
  • the examples that follow will also illustrate this contemplated use.
  • This example is intended to illustrate the reaction of a furan-formaldehyde resin with a commercially available phenolic no-bake resole.
  • the furan resin was prepared by reaction of furan and formaldehyde in a 4:1 molar ratio in the presence of oxalic acid heated at 100° C. for 2 hours. This mode of preparation is in accordance with the procedure outlined in the above mentioned Dunlop-Macander patent.
  • the resulting furan-formaldehyde resin had a viscosity of approximately 100 cps at room temperature.
  • IMC Self-Set 130 is a phenolic no-bake resole containing 15.6 percent free phenol, 15.4 percent water, and having a viscosity of 210 cps. To this mixture 2.4 parts of 75 percent solution of benzene sulfonic acid was added. In 3 minutes, the solution polymerized exothermically to a hard solid.
  • IMC Self-Set 130 (7.5 parts) and the furan-formaldehyde resin produced in accordance with Example 1 (22.5 grams) were admixed. To this mixture 2.4 grams of 75 percent benzene sulfonic acid was added. In six minutes the solution polymerized exothermically into a hard solid.
  • Example 2 This example is used to illustrate the contemplated use of a liquid resinous material prepared in accordance with the present invention, as outlined in the method of Example 1, as a foundry binder in the preparation of a hardened foundry shape.
  • the tensile strengths at various humidity levels and the bench life were measured using various ratios of phenolic no-bake binder (resoles) to furan-formaldehyde resin. The results are tabulated in Table I.
  • the binder consisting of an admixture of furan-formaldehyde resin prepared in accordance with the procedure described in Example 1 and the phenolic no-bake binder identified as IMC Self-Set 130 referred to in Example 1, is prepared using various ratios set forth in Table I. In each test, 0.15 percent of A1160 silane (T.M. of Union Carbide Corporation) a Ureido silane (50 percent in methanol) based on the weight of the binder, is added as an adhesion promoter, except as otherwise indicated in Table I.
  • A1160 silane T.M. of Union Carbide Corporation
  • Ureido silane 50 percent in methanol
  • the binder is then admixed with the acid catalyst-sand mix, and at the point where the binder is uniformly distributed in the sand mix, the resulting mixture is subjected to a bench life determination.
  • Simultaneously tensile test specimen biscuits (1 inch cross section) are prepared.
  • the bench life is determined by the use of a Dietert sand rammer.
  • the bench life is arbitrarily determined as the time at which the number of rams required to reach the preset volume is double the number of rams initially required to reach that volume.
  • the tensile strengths are run after overnight storage at the stated relative humidities set forth in the table.
  • the tensile strength number as set forth in Table I represents an average of 24 determinations, in each instance.
  • test 1--1 is not in accordance with this invention, but that test 1-2, test 1-3, and test 1-4 are in accordance with this invention.
  • the purpose of this example is to illustrate the results which occur when the concentration of phenol furan-formaldehyde resin prepared in accordance with the method set forth in Example 1 is varied with respect to another commercially available phenol resole resin.
  • the method as set forth in Example 3 was used, however, and the phenolic resole used in admixture with the furan-formaldehyde resin was Chem Set 700-P (T.M. of Thiem Corporation). Chem Set 700-P is reported to include 14-17 percent water, 1.4 percent of free formaldehyde, and 12.7 percent of free phenol.
  • the furan-formaldlehyde resin-phenolic resole binder mixture in accordance with the present invention is used at the level of 1.5 percent based on the weight of the sand.
  • the results of the tests on the sand mixture are shown in Table II.
  • This example is intended to show the results of varying the concentrations of furan-formaldehyde resin prepared in accordance with the method set forth in Example 1 to another phenolic resole resin. Again, the method as outlined in Example 2 was used, however, in this instance the phenolic resole resin was Chem-Rez 480 (T.M. of Ashland Chemical Company). The Chem-Rez 480 is reported to contain 4.5 percent free phenol, 15.4 percent water and has a viscosity of 530 cps. at ambient temperature.
  • furan-formaldehyde resins including those which do not cure readily under acidic conditions, are indeed readily cured in the presence of phenol resole resins in the presence of an acid catalyst. It is also apparent that the method in accordance with the present invention provides useful process for producing composite articles such as, for example, resin bound glass and sand articles including foundry sand shapes, for example.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Mold Materials And Core Materials (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
US05/806,661 1977-06-15 1977-06-15 Blends of furan-aldehyde resins with phenolic resins and molded articles produced therefrom Expired - Lifetime US4083817A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US05/806,661 US4083817A (en) 1977-06-15 1977-06-15 Blends of furan-aldehyde resins with phenolic resins and molded articles produced therefrom
GB12259/78A GB1588701A (en) 1977-06-15 1978-03-29 Curable furan-formaldehyde resin compositions and method of curing and using said compositions
BE1008815A BE865739A (fr) 1977-06-15 1978-04-06 Compositions durcissables de resines furanne-formaldehyde et procede de durcissement et d'utilisation de ces compositions
FR7810308A FR2394578A1 (fr) 1977-06-15 1978-04-06 Compositions durcissables de resines furanne-formaldehyde et procede de durcissement et d'utilisation de ces compositions
ES468590A ES468590A1 (es) 1977-06-15 1978-04-06 Metodo para curar una resina de furenoformaldehido.
NL7803778A NL7803778A (nl) 1977-06-15 1978-04-10 Furan-formaldehydehars bevattende materialen.
DE19782815909 DE2815909A1 (de) 1977-06-15 1978-04-10 Haertbare furan-formaldehyd-harzmassen und verfahren zum haerten und verwendung dieser massen
LU79407A LU79407A1 (fr) 1977-06-15 1978-04-10 Compositions durcissables de resines furanne-formaldehyde et procede de preparation,de durcissement et d'utilisation de ces compositions
IT48845/78A IT1102580B (it) 1977-06-15 1978-04-11 Processo per indurire ed usare composizioni resinose furan-formal deidiche e relative composizioni induribili
ES471856A ES471856A1 (es) 1977-06-15 1978-07-19 Metodo para preparar articulos compuestos tales como, por ejemplo, moldes de arena para fundicion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/806,661 US4083817A (en) 1977-06-15 1977-06-15 Blends of furan-aldehyde resins with phenolic resins and molded articles produced therefrom

Publications (1)

Publication Number Publication Date
US4083817A true US4083817A (en) 1978-04-11

Family

ID=25194548

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/806,661 Expired - Lifetime US4083817A (en) 1977-06-15 1977-06-15 Blends of furan-aldehyde resins with phenolic resins and molded articles produced therefrom

Country Status (9)

Country Link
US (1) US4083817A (it)
BE (1) BE865739A (it)
DE (1) DE2815909A1 (it)
ES (2) ES468590A1 (it)
FR (1) FR2394578A1 (it)
GB (1) GB1588701A (it)
IT (1) IT1102580B (it)
LU (1) LU79407A1 (it)
NL (1) NL7803778A (it)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256623A (en) * 1978-07-06 1981-03-17 Dynamit Nobel Aktiengesellschaft Binding agents prepared from resins containing adhesivizing agents of long shelf life
US4311619A (en) * 1980-04-14 1982-01-19 Aristo Corporation Cold set phenol-formaldehyde resin
US4516996A (en) * 1983-04-07 1985-05-14 Owens-Corning Fiberglas Corporation Formation of molded glass fiber parts from glass fiber blankets and product
US4619950A (en) * 1985-01-24 1986-10-28 Graphite Sales, Inc. Method and material for plugging an ingot mold
US4626560A (en) * 1981-10-08 1986-12-02 Union Carbide Corporation Novel binding agent compositions, foundry sand compositions and ureido functional organosilicon compounds
US4791022A (en) * 1983-11-07 1988-12-13 Owens-Corning Fiberglas Corporation Decorative panels

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3361841A (en) * 1966-09-26 1968-01-02 Hoechst Ag Binder composition comprising a mixture of a furan resin and an aromatic hydrocarbon-aldehyde condensate
US4017461A (en) * 1976-01-02 1977-04-12 The Quaker Oats Company Method for manufacturing liquid resinous furan-formaldehyde condensation products

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3361841A (en) * 1966-09-26 1968-01-02 Hoechst Ag Binder composition comprising a mixture of a furan resin and an aromatic hydrocarbon-aldehyde condensate
US4017461A (en) * 1976-01-02 1977-04-12 The Quaker Oats Company Method for manufacturing liquid resinous furan-formaldehyde condensation products

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256623A (en) * 1978-07-06 1981-03-17 Dynamit Nobel Aktiengesellschaft Binding agents prepared from resins containing adhesivizing agents of long shelf life
US4311619A (en) * 1980-04-14 1982-01-19 Aristo Corporation Cold set phenol-formaldehyde resin
US4626560A (en) * 1981-10-08 1986-12-02 Union Carbide Corporation Novel binding agent compositions, foundry sand compositions and ureido functional organosilicon compounds
US4516996A (en) * 1983-04-07 1985-05-14 Owens-Corning Fiberglas Corporation Formation of molded glass fiber parts from glass fiber blankets and product
US4791022A (en) * 1983-11-07 1988-12-13 Owens-Corning Fiberglas Corporation Decorative panels
US4619950A (en) * 1985-01-24 1986-10-28 Graphite Sales, Inc. Method and material for plugging an ingot mold

Also Published As

Publication number Publication date
DE2815909A1 (de) 1979-01-04
IT7848845A0 (it) 1978-04-11
GB1588701A (en) 1981-04-29
FR2394578A1 (fr) 1979-01-12
IT1102580B (it) 1985-10-07
ES468590A1 (es) 1978-11-16
LU79407A1 (fr) 1978-11-27
ES471856A1 (es) 1979-11-16
BE865739A (fr) 1978-10-06
NL7803778A (nl) 1978-12-19

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Legal Events

Date Code Title Description
AS Assignment

Owner name: CITIBANK, N.A., 641 LEXINGTON AVE., NEW YORK, NY 1

Free format text: LICENSE;ASSIGNOR:QO CHEMICALS, INC.,;REEL/FRAME:004255/0547

Effective date: 19840409

Owner name: QO CHEMICALS INC. CHICAGO ILLINOIS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:QUAKER OATS COMPANY A CORP OF NJ;REEL/FRAME:004253/0684

Effective date: 19840326

AS Assignment

Owner name: QO CHEMICALS, INC., 823 COMMERCE DRIVE, OAK BROOK,

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:004754/0123

Effective date: 19870209